|Publication number||US5009814 A|
|Application number||US 07/262,257|
|Publication date||Apr 23, 1991|
|Filing date||Oct 20, 1988|
|Priority date||Apr 8, 1987|
|Also published as||DE3711776A1, EP0285768A1, EP0285768B1|
|Publication number||07262257, 262257, US 5009814 A, US 5009814A, US-A-5009814, US5009814 A, US5009814A|
|Inventors||Heike Kelkenberg, Wulf Ruback, Klaus Engel|
|Original Assignee||Huls Aktiengesellschaft|
|Export Citation||BiBTeX, EndNote, RefMan|
|Patent Citations (8), Referenced by (114), Classifications (30), Legal Events (5)|
|External Links: USPTO, USPTO Assignment, Espacenet|
This application is a continuation of application Ser. No. 149,479, filed on Jan. 28,1988, now abandoned.
1. Field of the Invention
The invention is directed to the use of N-polyhydroxyalkyl fatty acid amides as thickening agents for liquid aqueous surfactant systems.
2. Discussion of the Background
The volume of production of liquid products in the cosmetics and detergents sector is continually increasing. In recent years the following products have particularly increased in importance: liquid shampoos, bubble baths, and shower preparations, i.e. liquid soaps for use in dispensers which deliver soap to the hand. Liquid dish washing detergents and liquid fine fabric detergents have also acquired substantial markets.
Any useful liquid surfactant formulation must meet the requirement of good shelf life. The liquid should not become turbid or produce sedimentation when subjected to temperature fluctuations. The product should have minimum tendency to have a defatting action on skin, and should not irritate skin.
A liquid surfactant system should have a viscosity which is suited to the intended application, and should be variable over as wide a range as possible.
Thus, viscosity is an important criterion for the quality of a liquid surfactant preparation. For example, for a douche gel one requires a very high viscosity, whereas for a shampoo one ordinarily desires a relatively liquid behavior with relatively low viscosity (1000-4000 mPa-sec).
Known thickeners for liquid surfactant formulations include, among others, nonionic fatty acid polyalkylene glycol esters, such as Antil® (molecular weight about 3000; provided by the firm Goldschmidt AG), as well as nonionic fatty acid alkanolamides, which have been used for many years (see 1958 J. Am. Oil Chemists' Soc., 35, 548). The preferred fatty acid alkanolamide is coconut oil fatty acid diethanolamide (Superamide®), which has thickening properties which are superior to those of other fatty acid diethanolamides.
The degree of thickening depends strongly on the surfactant system and on the electrolytes added. Thus, for example, it is known that when secondary paraffin-sulfonates are employed as surfactants in liquid preparations, problems are presented in adjusting the viscosity. The known commercially available thickeners mentioned above have insufficient thickening action in systems with secondary paraffinsulfonates in the presence of electrolytes. Viscosity adjusting problems also occur when surfactant mixtures containing paraffinsulfonates are employed as often recommended, e.g. paraffinsulfonate with ether sulfate. See 1976, Fette--Seifen--Anstrichmittel, 78, 200.
Accordingly, one object of the present invention is to provide a thickener for liquid aqueous surfactant systems which satisfies the practical requirements of surfactant, electrolyte, and application.
Another object of the invention is to provide a thickener which gives good results in the presence of secondary paraffinsulfonates as surfactants.
These and other objects which will become apparent from the following specification have been achieved by the present liquid aqueous surfactant composition comprising (a) an aqueous liquid surfactant, and (b) an N-polyhydroxyalkyl fatty acid amide of the formula: ##STR2## where R1 is an alkyl group, optionally branched, with 1-17, preferably 7-17 carbon atoms;
R2 is hydrogen, or an alkyl group, optionally branched and/or unsaturated, with 1-18, preferably 1-6 carbon atoms, or a group ##STR3## with n=0 to 5, and R3 is hydrogen or --CH3 ; and X is a polyhydroxyalkyl group with 4-7 carbon atoms, which may be glycosidically linked with a mono-, di-, or oligosaccharide group.
FIG. 1 shows the effect of N-methyl coconut oil fatty acid glucamide and sodium chloride. Concentration of surfactant (10% by wt. in H2 O), 3 parts by wt. ether sulfate, 1 part by wt. paraffin sulfonate. The data points indicated by squares show a composition without fatty acid amide. The dotted line shows 3% coconut oil fatty acid diethanolamide. The trianges show 5% coconut oil fatty acid diethanolamide. The crosses show 3% N-methyl coconut oil fatty acid glucamide. The circles show 5% N-methyl coconut oil fatty acid glucamide.
FIG. 2 illustrates the gentleness to skin of mixtures of paraffin sulfonate and N-methyl coconut oil fatty acid (x . . . x) and N-methyl lauric acid glucamide (o . . . o). Zein test according to Goette.
R2 is hydrogen, or an alkyl group, optionally branched and/or unsaturated, with 1-18, preferably 1-6 carbon atoms, or a group with n=0 to 5, and R3 is hydrogen or --CH3; and
X is a polyhydroxyalkyl group with 4-7 carbon atoms, which may be glycosidically linked with a mono-, di-, or oligosaccharide group.
The inventively employed N-polyhydroxyalkyl fatty acid amides should be present in an amount of 0.5-30 wt.%, preferably 0.5-10 wt.%, based on the weight of the entire liquid surfactant system.
They may possibly be employed in combination with known thickeners.
In general formula I, the alkyl group R1 may be derived from, e.g., the following carboxylic acids: octanoic acid, decanoic acid, lauric acid, myristic acid, palmitic acid, and stearic acid.
Also in formula I, R2 may be, e.g., methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, n-pentyl, isopentyl, n-hexyl, isohexyl, n-octyl, 2-ethylhexyl, n-nonyl, isononyl, n-decyl, isodecyl, dodecyl, tridecyl, tetradecyl, hexadecyl, stearyl, 2-hydroxyethyl, or 2-hydroxypropyl.
X may be the following polyhydroxyalkyl groups: 1-desoxyerythrityl, 1-desoxyarabityl, 1-desoxyxylityl, 1-desoxysorbityl, 1-desoxysorbit-2-yl, 1-desoxymannityl, 2-desoxymannit-2-yl, 1desoxygalactityl, 1-desoxy-4-glucosido-sorbityl, 1-desoxy-4-galactosido-sorbityl, 2-desoxy-4-glucosido-sorbit-2-yl, 2-desoxy-4-glucosido-mannit-2-yl, 1-desoxy-4-maltoglucosido-sorbityl, 1-desoxy-4-oligoglucosido-sorbityl, 1-desoxy-4-polyglucosidosorbityl. X is preferably a 1-desoxysorbityl group.
The following compounds are candidates as inventively employed thickeners: N-methyl coconut oil fatty acid glucamide, stearic acid lactamide, N-methyloleic acid maltamide, N-(2-hydroxyethyl)-lauric acid xylamide, N-ethylmyristic acid galactamide, N-lauryl-N-(4-oligoglucosidosorbityl)-decanoamide, and N-propyl-N-(2-desoxysorbit-2-yl)decanoamide.
Examples of surfactants which may be present in the liquid aqueous surfactant systems are:
(a) anionic surfactants, e.g. alkylarylsulfonates, particularly alkylbenzenesulfonates, olefinsulfonates, secondary paraffinsulfonates, sulfosuccinic acid half ester salts, fatty alcohol ether sulfates;
(b) nonionic surfactants, e.g. fatty alcohol polyglycol ethers, alkylphenol polyglycol ethers, fatty acid polyglycol esters, polypropylene oxide/polyethylene oxide mixed polymers; etc.
An important advantage of the inventively employed class of compounds over currently employed fatty acid diethanolamides is their high adaptability to being adjusted to the given requirements of the surfactant system, by variation of the three substituents R1, R2, and X.
Whereas in the ordinarily employed fatty acid diethanolamides only the alkyl chain of the fatty acid is variable, in the present class of materials there is variability of the hydrophobic N-substituent R2 and the hydrophilic carbohydrate group X, as well as of the fatty acid alkyl chain R1. This enables the thickener to be carefully matched to the liquid surfactant system.
Compounds of formula I are prepared by known means, by reacting fatty acids or fatty acid esters with polyhydroxyalkylamines (which may be N-substituted), in the melt, possibly in the presence of alkaline catalysts.
The polyhydroxyalkylamines are themselves prepared by the widely known method of reductive amination of sugar derivatives using liquid ammonia or other alkylamines (e.g. methylamine, ethylamine, octylamine, laurylamine, coconut oil fatty acid amine, stearylamine, or the alkanolamines, ethanolamine and isopropanolamine). Examples of possible sugar derivatives are: erythrose, arabinose, glucose, galactose, mannose, fructose, xylose, maltose, lactose, saccharose, cellobiose, maltotriose, maltodextrin, and other breakdown products of starch, e.g. glucose syrup.
Other features of the invention will become apparent in the course of the following descriptions of exemplary embodiments which are given for illustration of the invention and are not intended to be limiting thereof.
In a stirred flask, 669 g (3.0 mol) coconut oil fatty acid methyl ester and 585 g (3.0 mol) N-methylglucamine were heated with gradual addition of 3.3 g sodium methanoate at 135° C. The methanol formed during the reaction was condensed in a cooled receiver under vacuum increasing from 100 to 15 mbar. After methanol evolution ceased, the reaction mixture was dissolved in 1.5 liter hot isopropanol, filtered, and crystallized. After filtration and drying, 882 g (72% of theoretical) of waxy N-methyl coconut oil fatty acid
glucamide was obtained. Softening point: 80°-84° C. Base number: 4 mg KOH/g.
The following fatty acid glucamides were prepared analogously:
TABLE I______________________________________ Base Softening number point (mg Yield (° C.) KOH/g)______________________________________N-methyllauric acid glucamide: 76% 94-96 6N-methylmyristic acid glucamide: 75% 98-100 3N-methylpalmitic acid glucamide: 75% 103-105 5N-methylstearic acid glucamide: 84% 96-98 6______________________________________
The measurements were carried out for N-methyl coconut oil fatty acid glucamide.
As a Comparison Example, a thickener according to the prior art was used, e.g. coconut oil fatty acid diethanolamide (Marlamid DF 1218® provided by Huels AG), or the commercial product Antil 141®, a polyoxyethylene propylene glycol dioleate, provided by the firm Goldschmidt.
The same technique was used for all the viscosity measurements.
Measuring apparatus: Rotovisco RV 12, computer controlled, supplied by the firm Haake.
Measuring system: MV D1N.
Range of shears: 0-50 sec-1.
Temperature: 25° C.
Surfactant, and concentration:
10% mixture of 3 parts fatty alcohol ether sulfate (MARLINAT 24/28® Huels AG); and 1 part paraffinsulfonate (MARLON PS 60®. Huels AG).
The N-methyl coconut oil fatty acid glucamide had the following formula: ##STR4## where n=6 to 16.
Coconut oil fatty acid diethanolamide gave better results in an ether sulfate/paraffin sulfate mixed system as shown in FIG. 1.
In a shampoo formula with the glucamine salt of paraffinsulfonic acid as the main surfactant, which is particularly gentle to skin, N-methyl coconut oil fatty acid glucamide had a surprising synergistic effect in combination with the known thickener Antil 141® (supplied by Goldschmidt AG) which has no thickening action when used alone or with coconut oil fatty acid diethanolamide in a system with paraffinsulfonate salts (see Table II). Formulations with fatty acid glucamides have good shelf life. The compatibility of paraffinsulfonates with human skin is substantially improved by addition of fatty acid glucamides (see FIG. 2).
TABLE II______________________________________Shampoo formulations based on aparaffinsulfonic acid sodium salt or aparaffinsulfonic acid glucamine salt (whichis gentle to skin), in combination withmixtures of thickeners I II IIIFormula (%) (%) (%)______________________________________Paraffinsulfonic acid, 13.5 13.5 13.5glucamine saltMarlamid ® (coconut oil 3.0fatty acid diethanolamideN-methyl coconut oil fatty 3.0acid glucamideAntil ® (polyoxyethylene- 2.56 2.56 2.56propylene glycol dioleateViscosity (mPa.S) 142 317 1,590Paraffinsulfonic acid, 13.5 13.5 13.5sodium saltMarlamid ® 3.0N-methyl coconut oil fatty 3.0acid glucamideAntil ® 2.56 2.56 2.56Viscosity (mPa.S) 63 217 622______________________________________
The tests clearly show the superiority of the inventively employed N-polyhydroxyalkyl fatty acid amides over conventional thickeners, not only in thickening action but also in gentleness to skin.
Obviously, numerous modifications and variations of the present invention are possible in light of the above teachings. It is therefore to be understood that within the scope of the appended claims, the invention may be practiced otherwise than as specifically described herein.
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|U.S. Classification||132/202, 510/128, 424/70.24, 510/126, 424/70.31|
|International Classification||A61K8/00, A61K8/46, A61K8/42, C11D17/00, A61Q5/00, B01F17/22, A61Q5/02, C11D3/37, C11D1/52, B01F17/00, A61Q19/10, C09K3/00, C11D3/32|
|Cooperative Classification||A61K8/42, C11D3/32, A61K8/466, C11D17/003, C11D1/525, A61Q5/02|
|European Classification||A61Q5/02, C11D1/52H, C11D17/00B, A61K8/42, C11D3/32, A61K8/46F|
|Jul 24, 1990||AS||Assignment|
Owner name: HULS AKTIENGESELLSCHAFT, D-4370 MARL, WEST GERMANY
Free format text: ASSIGNMENT OF ASSIGNORS INTEREST.;ASSIGNORS:KELKENBERG, HEIKE;RUBACK, WULF;ENGEL, KLAUS;REEL/FRAME:005390/0634;SIGNING DATES FROM 19871227 TO 19871230
|Sep 27, 1994||FPAY||Fee payment|
Year of fee payment: 4
|Nov 17, 1998||REMI||Maintenance fee reminder mailed|
|Apr 25, 1999||LAPS||Lapse for failure to pay maintenance fees|
|Jun 22, 1999||FP||Expired due to failure to pay maintenance fee|
Effective date: 19990423